Thermosetting resin composition and adhesive film

ABSTRACT

The invention provides a thermosetting resin composition comprising components (A) and (B), wherein the sum of components (A) and (B) is 90% by weight or more based on the composition; an adhesive film obtained from the composition; and a laminate obtained by laminating the film and an adherent and thermally curing the resultant. Component (A) is an amino acid or imidazoles, and component (B) is an epoxy group-containing ethylene copolymer obtained by polymerizing (b 1 ) and (b 2 ), wherein (b 1 ) is ethylene or propylene, and (b 2 ) is a monomer represented by formula (1):  
                 
wherein R represents a hydrocarbon group of a carbon number of 2-18 having a double bond, wherein at least one of hydrogen atoms of the hydrocarbon group may be substituted with a halogen atom, a hydroxyl group or a carboxyl group, and X represents a single bond or a carbonyl group).

FIELD OF THE INVENTION

The present invention relate to a thermosetting resin compositioncomprising an amino acid or imidazoles, and an epoxy group-containingethylene-based copolymer; an adhesive film obtained from thecomposition; and a laminate obtained by laminating the adhesive filmwith an adherent and then thermally curing the resultant.

BACKGROUND ART

In recent years, in the field of electric and electronic parts, thinningand down-sizing are being progressed, semiconductor encapsulatingmaterials, electronic part encapsulating materials for solar cells andEL (electroluminescence) lamps, die bonding sheets between integratedcircuit/substrate, and adhesives for electric and electronic part suchas an interlayer insulating layer between substrates require low elasticmodulus and a thinner film in addition to heat resistance to solder(hereinafter, referred to as solder heat resistance). In order tosimplify a procedure of manufacturing electric and electronic parts, dryfilm-shaped form is required as a form before curing of an adhesive.

On the other hand, JP-A No. 2001-240838 discloses that a dry film-shapedadhesive (adhesive film) is obtained by dissolving a resin compositionof an epoxy resin, an epoxy curing agent, an epoxy group-containingethylene copolymer and imidazoles in an organic solvent, then coatingthe solution and drying the solvent.

DISCLOSURE OF THE INVENTION

An object of the present invention is to provide a thermosetting resincomposition which can be directly molded in a dry film-shape withoutsteps of dissolution in an organic solvent, coating and drying; anadhesive film obtained by extrusion-molding the composition; and alaminate excellent in adhesive property and solder heat resistance whichis obtained by bonding the adhesive film obtained and an adherent suchas electric and electronic parts.

That is, the present invention relates to the following:

<1> A thermosetting resin composition comprising component (A) andcomponent (B) below, wherein the sum of the content of the component (A)and component (B) is 90% by weight or more based on the composition;

component (A): at least one selected from amino acids and imidazoles,and component (B): an epoxy group-containing ethylene copolymer obtainedby polymerizing monomer (b₁) and monomer (b₂) below:

monomer (b₁): at least one selected from ethylene and propylene, and

monomer (b₂): a monomer represented by formula (1) below:

(wherein R represents a hydrocarbon group of a carbon number of from 2to 18 having a double bond, at least one of hydrogen atoms of thehydrocarbon group may be substituted with a halogen atom, a hydroxylgroup or a carboxyl group, and X represents a single bond or a carbonylgroup.)

<2> The thermosetting resin composition according to the above <1>,wherein the content of a structural unit derived from monomer (b₂) is 1to 30 parts by weight relative to 100 parts by weight of component (B).

<3> The thermosetting resin composition according to the above <1> or<2>, wherein the content of a structural unit derived from monomer (b₁)is 30 to 75 parts by weight relative to 100 parts by weight of component(B).

<4> The thermosetting resin composition according to any one of theabove <1> to <3>, wherein component (B) is a copolymer obtained bypolymerizing monomer (b₁), monomer (b₂) and monomer (b₃) below:

monomer (b₃): a monomer which has a functional group copolymerizablewith ethylene, does not have a functional group reactive with an epoxygroup, and is different from either of monomer (b₁) and monomer (b₂).

<5> The thermosetting resin composition according to any one of theabove <1> to <4>, wherein the ratio by weight of component (A) andcomponent (B) ((A)/(B)) is from 0.1/99.9 to 10/90.

<6> The thermosetting resin composition according to any one of theabove <1>to <5>, which further contains component (C) below:

component (C): an antioxidant.

<7> The thermosetting resin composition according to <6>, whereincomponent (C) is at least one selected from the group consisting of aphenolic antioxidant, a phosphoric antioxidant and a sulfuricantioxidant.

<8> The thermosetting resin composition according to any one of theabove <1> to <7>, wherein component (A) is an amino acid, and the aminoacid is at least one selected from aminoacetic acid, β-alanine,4-aminobutyric acid, aminovalerianic acid, 6-aminohexanoic acid,11-aminoundecanoic acid and 12-aminododecanoic acid.

<9> The thermosetting resin composition according to any one of theabove <1> to <7>, wherein component (A) is an imidazole, and theimidazole is at least one selected from1-cyanoethyl-2-ethyl-4-methylimidazolium trimellitate,1-cyanoethyl-2-undecylimidazolium trimellitate,1-cyanoethyl-2-phenylimidazolium trimellitate,2,4-diamino-6-[2′-methylimidazolyl-(1′)]-ethyl-s-triazine,2,4-diamino-6-(2′-undecylimidazolyl)-ethyl-s-triazine,2,4-diamino-6-[2′-ethyl-4-methylimidazolyl-(1′)]-ethyl-s-triazine, anadduct of 2,4-diamino-6-[2′-methylimidazolyl-(1′)]-ethyl-s-triazine withisocyanuric acid, an adduct of 2-phenylimidazole with isocyanuric acid,and an adduct of 2-methylimidazole with isocyanuric acid.

<10> An adhesive film comprising the thermosetting resin compositionaccording to any one of the above <1> to <9>.

<11> The adhesive film according to the above <10>, which is obtained byextrusion-molding the thermosetting resin composition according to anyone of the above <1> to <9>.

<12> An adhesive film, which is obtainable by further irradiating anelectron beam on the adhesive film according to the above <10> or <11>.

<13> The adhesive film according to the above <12>, which is obtainableby performing the electron beam irradiation plural times.

<14> A laminate, which is obtainable by laminating the adhesive filmaccording to any one of the above <10> to <13>with an adherent, andthermally curing the resultant.

BEST MODE FOR CARRYING OUT THE INVENTION

The thermosetting resin composition of the present invention(hereinafter, referred to as the present composition) is characterizedin that it contains the aforementioned component (A) and component (B),and the sum of the content of component (A) and component (B) is 90% byweight or more based on the composition.

Component (A) used in the present invention is at least one selectedfrom amino acids and imidazoles.

Herein, the amino acid is a compound having an amino group and acarboxyl group, and its specific example includes aminoacetic acid,D-alanine, L-alanine, DL-alanine, β-alanine, L-2-aminoadipic acid,L-α-aminoadipic acid, o-aminobenzoic acid, m-aminobenzoic acid,p-aminobenzoic acid, D-(−)-2-aminobutyric acid, DL-2-aminobutyric acid,L-(+)-2-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid,DL-3-aminoisobutyric acid, aminovalerianic acid, DL-α-aminocaprylicacid, ω-aminocaprylic acid, 1-aminocyclobutane carboxylic acid,1-amino-1-cyclohexane carboxylic acid, 2-amino-1-cyclohexane carboxylicacid, 2-amino-4-cyclohexene-1-carboxylic acid, 1-amino-i-cyclopentanecarboxylic acid, 2-amino-i-cyclopentane carboxylic acid,1-amino-1-cyclopropane carboxylic acid, DL-2-aminohexanoic acid,6-aminohexanoic acid, DL-1-aminoindane-1-carboxylic acid,2-aminoisobutyric acid, 5-aminoisophtalic acid, 2-amino-3-methylbenzoicacid, 2-amino-4-methylbenzoic acid, 2-amino-5-methylbenzoic acid,2-amino-6-methylbenzoic acid, 4-amino-3-methylbenzoic acid,2-amino-2-methylbutanedionic acid, 2-amino-2-methylbutanoic acid,2-amino-4-methylpentanedionic acid, 3-amino-4-methylpetanoic acid,2-amino-2-methyl-3-phenylpropanoic acid, 2-aminopentanoic acid,p-aminophenylacetic acid, a-aminophenylacetic acid,2-amino-4-phenylbutyric acid, 3-amino-3-phenylpropionic acid,11-aminoundecanic acid, 12-aminododecanoic acid and the like.

Among these, it is preferred to use at least one selected fromaminoacetic acid, β-alanine,4-aminobutyric acid, aminovalerianic acid,6-aminohexanoic acid, 11-aminoundecanoic acid and 12-aminododecanoicacid, and in particular, it is more preferred to use 12-aminododecanoicacid.

As the amino acid, commercially available amino acids such as “K-37Y”(12-aminododecanoic acid, manufactured by P.T.I. Japan Co., Ltd.) may beused as they are.

The imidazoles as component (A) is a compound having an imidazoleskeleton, and their specific examples include 2-methylimidazole,2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole,2-ethyl-4-methylimidazole, 2-phenylimidazole,2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole,1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole,1-cyanoethyl-2-ethylimidazole, 1-cyanoethyl-2-undecylimidazole,1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazoliumtrimellitate, 1-cyanoethyl-2-undecylimidazolium trimellitate,1-cyanoethyl-2-phenyl-imidazolium trimellitate,2,4-diamino-6-[2′-methylimidazolyl-(1′)]-ethyl-s-triazine,2,4-diamino-6-(2′-undecylimidazolyl)-ethyl-s-triazine,2,4-diamino-6-[2′-ethyl-4-methylimidazolyl-(1′)]-ethyl-s-triazine, anadduct of 2,4-diamino-6-[2′-methylimidazolyl-(1′)]-ethyl-s-triazine withisocyanuric acid, an adduct of 2-phenylimidazole with isocyanuric acid,and an adduct of 2-methylimidazole with isocyanuric acid,2-phenyl-4,5-dihydroxymethylimidazole,2-phenyl-4-methyl-5-hydroxymethylimidazole,1-cyanoethyl-2-phenyl-4,5-di(2-cyanoethoxy)methylimidazole,2-methylimidazoline, 2-phenylimidazoline,1-dodecyl-2-methy-3-benzylimidazolium chloride,1-benzyl-2-phenylimidazole hydrochloride, 1-benzyl-2-phenylimidazoliumtrimellitate, and the like.

Further, as component (A), imidazoles which are commercially sold astrade marks such as, for example, “CUREZOLE C11Z-A”(2,4-diamino-6-(2′-undecylimidazolyl)-ethyl-s-triazine, manufactured byShikoku Kasei Co., Ltd.) and “CUREZOLE 2PZ-OK” (an adduct of2-phenylimidazole with isocyanuric acid, manufactured by Shikoku KaseiCo., Ltd.) may be used as they are.

Among the above-mentioned imidazoles as component (A), in particular,from the viewpoint of the thermal stability and aging stability of theresulting thermosetting resin composition, it is preferred to use1-cyanoethyl-2-ethyl-4-methylimidazolium trimellitate,1-cyanoethyl-2-undecylimidazolium trimellitate,1-cyanoethyl-2-phenylimidazolium trimellitate,2,4-diamino-6-[2′-methylimidazolyl-(1′)]-ethyl-s-triazine,2,4-diamino-6-(2′-undecylimidazolyl)-ethyl-s-triazine,2,4-diamino-6-[2′-ethyl-4-methylimidazolyl-(1′)]-ethyl-s-triazine, anadduct of 2,4-diamino-6-[2′-methylimidazolyl-(1′)]-ethyl-s-triazine withisocyanuric acid, an adduct of 2-phenylimidazole with isocyanuric acid,an adduct of 2-methylimidazole with isocyanuric acid and the like.

Component (B) used in the present invention is an epoxy group-containingethylene copolymer obtained by polymerizing

at least one monomer (hereinafter, described as monomer (b₁)) selectedfrom ethylene and propylene and

a monomer (hereinafter, referred to as monomer (b₂)) represented byformula (1) below:

(wherein R represents a hydrocarbon group of a carbon number of from 2to 18 having a double bond, at least one of hydrogen atoms of thehydrocarbon group may be substituted with a halogen atom, a hydroxylgroup or a carboxyl group and X represents a single bond or a carbonylgroup.

Inter alia, as the monomer (b₁), ethylene is preferable.

In formula (1), examples of substituent R include substituentsrepresented by formulas (2) to (8) below:

In addition, X in the formula (1) represents a single bond in which theoxygen atom and substituent R in formula (1) are directly bound witheach other, or a carbonyl group.

Specific examples of monomer (b₂) include unsaturated glycidyl ethersuch as allylglycidyl ether, 2-methylallyglycidyl ether andstyrene-p-glycidyl ether; and unsaturated glycidyl esters such asglycidyl acrylate, glycidyl methacrylate and itaconic acid glycidylester.

The content of structural unit derived from monomer (b₂) may be about 1to about 30 parts by weight relative to 100 parts by weight of component(B). When the structural unit derived from monomer (b₂) is 1 part byweight or more, there is a tendency that adherability of the resultingadhesive film is improved, which is preferred. When the structural unitis 30 parts by weight or less, there is a tendency that a mechanicalstrength of the resulting adhesive film is improved, which is alsopreferred.

In addition, the content of structural unit derived from monomer (b₁) ispreferably about 30 to about 99 parts by weight relative to 100 parts byweight of component (B).

For example, by polymerizing monomer (b₁) and monomer (b₂) with amonomer (hereinafter, referred to as monomer (b₃)) which is differentfrom either of monomer (b₁) and monomer (b₂) and has a functional groupcopolymerizable with ethylene such as a vinyl group and an alkylenegroup, then component (B) may contain a structural unit derived frommonomer (b₃) in addition to a structural unit derived from monomer (b₁)and a structural unit derived from monomer (b₂). It is noted thatmonomer (b₃) should not substantially contain a functional group (whichcan react with an epoxy group) such as a carboxyl group (—COOH) and anacid anhydride group (—CO—O—CO—), but may contain an ester group sincethe ester group does not react with an epoxy group.

Specific examples of monomer (b₃) include an α,β-unsaturated carboxylicacid alkyl ester having an alkyl group of a carbon number of about 3 toabout 8 (such as methyl acrylate, ethyl acrylate, n-propyl acrylate,isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutylacrylate, methyl methacrylate, ethyl methacrylate, n-propylmethacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butylmethacrylate and isobutyl methacrylate); a vinyl ester with a carboxylicacid of a carbon number of about 2 to about 8 (such as vinyl acetate,vinyl butyrate, vinyl propionate, vinyl pivalate, vinyl laurate, vinylisononanate and vinyl versatate); an α-olefins of a carbon number ofabout 4 to about 20 (such as 1-butene and isobutene); a diene compoundof a carbon number of about 3 to about 20 (such as butadiene, isopreneand cyclopentadiene); a vinyl compound of a carbon umber of about 2 toabout 20 (such as vinyl chloride, styrene, acrylonitrile,methacrylonitrile, acrylamide and methacrylamide).

As monomer (b₃), inter alia, vinyl acetate, methyl acrylate, ethylacrylate, n-butyl acrylate and methyl methacrylate are preferred.

The content of structural unit derived from monomer (b₃) may be about 0to about 70 parts by weight, and is preferably about 5 to about 60 partsby weight, relative to 100 parts by weight of component (B). When thecontent is 70 parts by weight or smaller, there is a tendency thatcomponent (B) can be easily prepared by a high pressure radical method,which is preferred.

Component (B) may be any of a block copolymer, a graft copolymer, arandom copolymer and an alternating copolymer. Examples thereof includea copolymer obtained by grafting monomer (b₂) onto a propylene-ethyleneblock copolymer described in Japanese Patent No.2632980 (correspondingto U.S. Pat. No. 5,032,459) and a copolymer obtained by graftingα,β-unsaturated carboxylic acid ester onto a copolymer (described inJapanese Patent No.2600248) of ethylene and an epoxy group-containingmonomer.

Examples of a process for preparing component (B) in the presentinvention include:

a method of copolymerizing a monomer as a raw material under a pressureof from about 500 to about 4000 atm at a temperature of from about 100to about 300° C. in the presence of ethylene and a radical generator,and also in the presence or the absence of a proper solvent or a chaintransfer agent; and

a method of mixing a monomer such as monomer (b₂) as a raw material anda radical generator with a polyethylene resin and thenmelt-graft-copolymerizing the resulting mixture in an extruder.

Herein, the polyethylene resin may be a homopolymer of monomer (b₁), ora copolymer of monomer (b₃) and monomer (b₁), or the like.

Component (B) in the present invention preferably has a MFR (melt flowrate; measured in accordance with JIS K7210) of from about 30 g to about1000 g per 10 minutes, and more preferably has a MFR of from about 50 gto about 500g per 10 minutes, under the conditions of 2.16 kg load at atemperature of 190° C. When the MFR is 30 g/10 minutes or larger, thereis a tendency that flowability of the resulting thermosetting resincomposition is improved so that, even when there are irregularities on asurface of an adherent, they are easily embedded, which is preferred. Onthe other hand, when the MFR is 1000 g/10 minutes or smaller, there is atendency that solder heat resistance of the resulting thermosettingresin composition is improved, which is also preferred.

Component (B) may be commercially available one, and examples thereofinclude “Bondfast (registered trade mark)” series (manufactured bySumitomo Chemical Co., Ltd.), “Sepolsion G (registered trademark)”series (manufactured by Sumitomo Seika Chemicals Co., Ltd.) and“Rexpearl RA (registered trade mark)” series (manufactured by NipponPolyolefin K.K.).

The present composition can be obtained by mixing component (A) andcomponent (B), and component (A) and component (B) may be compatiblewith each other in the present composition. Further, the sum of thecontent of component (A) and component (B) is 90% by weight or more,preferably 95% by weight or more and more preferably 99% by weight ormore, based on the present composition.

The ratio by weight of component (A) to component (B) ((A)/(B)) may befrom 0.1/99.9to about 10/90, and is preferably from 0.5/99.5 to 6/94.

In addition, the present composition may contain a promoter for curingan epoxy resin, such as an organic phosphorus compound, in addition tocomponent (A) and component (B) in order to promote a curing reaction ofthe component (A) and component (B).

By inclusion of an antioxidant as component (C) in addition to component(A) and component (B) in the present composition, there is a tendencythat, when the composition is molded into a film, occurrence ofun-uniform foreign matter called “fish eye” is suppressed, and storagestability of the composition and the resulting adhesive film obtainedfrom the composition is improved. Therefore, component (C) is preferablycontained.

Examples of component (C) include a phenolic antioxidant, a phosphoricantioxidant, a sulfuric antioxidant, and an amine antioxidant. As theantioxidant, two or more kinds of antioxidants may be used by combiningthem. Inter alia, from a viewpoint of gel-preventing effect andcoloring, it is preferred to use any of a phenolic antioxidant, aphosphoric antioxidant and a sulfuric antioxidant.

Examples of the phenolic antioxidant include2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol,2,6-dicyclohexyl-4-methylphenol, 2,6-di-t-amyl-4-methylphenol,2,6-di-t-octyl-4-n-propylphenol, 2,6-dicyclohexyl-4-n-octylphenol,2-isopropyl-4-methyl-6-t-butylphenol, 2-t-butyl-2-ethyl-6-t-octylphenol,2-isobutyl-4-ethyl-6-t-hexylphenol,2-cyclohexyl-4-n-butyl-6-isopropylphenol, dl-α-tocopherol,t-butylhydroquinone, 2,2′-methylenebis(4-methyl-6-t-butylphenol),4,4′-butylidenebis(3-methyl-6-t-butylphenol),4,4′-thiobis(3-methyl-6-t-butylphenol),2,2′-thiobis(4-methyl-6-t-butylphenol),4,4′-methylenebis(2,6-di-t-butylphenol),2,2′-methylenebis[6-(1-methylcyclohexyl)-p-cresol],2,2′-ethylidenebis(4,6-di-t-butylphenol),2,2′-butylidenebis(2-t-butyl-4-methylphenol),2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methyl-phenylacrylate,2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl)-4,6-di-t-pentylphenylacrylate,1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, triethylene glycolbis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediolbis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],2,2-thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate],N,N′-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamide),3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester,tris(2,6-dimethyl-3-hydroxy-4-t-butylbenzyl) isocyanurate,tris(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate,tris[(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate,tris(4-t-butyl-2,6-dimethyl-3-hydroxybenzyl)isocyanurate,2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine,tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionatelmethane,2,2′-methylenebis(4-methyl-6-t-butylphenol) terephthalate,1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)-benzene,3,9-bis[1,1-dimethyl-2-(f-(3-t-butyl-4-hydroxy-5-methyl-phenyl)propionyloxy)ethyl]-2,4,8,10-tetraoxaspiro[5,5]-undecane,2,2-bis[4-(2-(3,5-di-t-butyl-4-hydroxyhydrocinnamoyloxy))-ethoxyphenyl]propane,and β-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid stearyl ether.

Among them, β-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid stearylester,tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionatelmethane,tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)-benzene,dl-α-tocopherol, tris(2,6-dimethyl-3-hydroxy-4-t-butylbenzyl)isocyanurate,tris[(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxyethyl]-isocyanurate,and3,9-bis[1,1-dimethyl-2-{f-(3-t-butyl-4-hydroxy-5-methyl-phenyl)propionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5,5]-undecaneare preferable.

As the phenolic antioxidant, commercially available phenolicantioxidants may be used, and examples of such a commercially availablephenolic antioxidants include Irganox 1010 (manufactured by CibaSpecialty Chemicals), Irganox 1076 (manufactured by Chiba SpecialtyChemicals), Irganox 1330 (manufactured by Chiba Specialty Chemicals),Irganox 3114 (manufactured by Chiba Specialty Chemicals), Irganox 3125(manufactured by Chiba Specialty Chemicals), Sumilizer BHT (manufacturedby Sumitomo Chemical Co., Ltd.), Cyanox 1790 (manufactured by Cytech),Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.), andvitamin E (manufactured by Esai).

As the phenolic antioxidant, two or more of phenolic antioxidants may beused.

Examples of the phosphoric antioxidant include trioctyl phosphite,trilauryl phosphite, tridecyl phosphite, (octyl)diphenyl phosphite,tris(2,4-di-t-butylphenyl) phosphite, triphenyl phosphite,tris(butoxyethyl) phosphite, tris(nonylphenyl) phosphite,distearylpentaerythritol diphosphite,tetra(tridecyl)-1,1,3-tris(2-methyl-5-t-butyl-4-hydroxy-phenyl)butanediphosphite, tetra(C₁₂˜C₁₅ mixed alkyl)-4,4′-isopropylidenediphenyldiphosphite,tetra(tridecyl)-4,4′-butylidenebis(3-methyl-6-t-butyl-phenol)diphosphite,tris(3,5-di-t-butyl-4-hydroxyphenyl) phosphite, tris(mono-, di-mixednonylphenyl) phosphite, hydrogenated-4,4′-isopropylidenediphenolpolyphosphite,bis(octylphenyl)bis[4,4′-butylidenebis(3-methyl-6-t-butyl-phenol)]-1,6-hexanedioldiphosphite, phenyl(4,4′-isopropylidenediphenol)pentaerythritoldiphosphite, distearylpentaerythritol diphosphite,tris[4,4′-isopropylidenebis(2-t-butylphenol)]phosphite,di(isodecyl)phenyl phosphite,4,4′-isopropylidenebis(2-t-butylphenol)bis(nonylphenyl)phosphite,9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,bis(2,4-di-t-butyl-6-methylphenyl)ethyl phosphite,2-[{2,4,8,10-tetra-t-butyldibenz[d,f][1.3.21-dioxaphosphepin-6-yl}oxy]-N,N-bis[2-[(2,4,8,10-tetra-t-butyldibenz[d,f][1.3.2]-dioxaphosphepine-6-yl)oxy)ethyl]ethaneamine,6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxyl-2,4,8,10-tetra-t-butyldibenz[d,f][1.3.2]-dioxaphosphepine.

In addition, other example compounds as the phosphoric antioxidant, suchas bis(dialkylphenyl)pentaerythritol diphosphite ester, include aspiro-type compound represented by formula (9) below:

(wherein R¹, R² and R³ represent independently a hydrogen atom or analkyl group of a carbon number of from 1 to about 9), and a cage-typecompound represented by formula (10) below:

(wherein R⁴, R⁵ and R⁶ represent independently a hydrogen atom or analkyl group of a carbon number of from 1 to about 9).

As such a phosphite ester, usually, a mixture of compounds representedby formulas (9) and (10) may be used.

When substituents R¹ to R⁶ are alkyl groups, then branched alkyl groupsare preferred and, inter alia, t-butyl groups are preferred.

In addition, as a position of substituents R¹ to R⁶ in the phenylgroups, 2, 4 and 6 positions are preferred.

Specific examples of phosphite ester as a phosphoric antioxidant includebis(2,4-di-t-butylphenyl)pentaerythritol diphosphite,bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite,bis(nonylphenyl)pentaerythritol diphosphite and the like. In addition,examples of a phosphoric antioxidant, which is a phosphonite having astructure in which carbon and phosphorus are directly bound, include acompound such astetrakis(2,4-di-t-butylphenyl)-4,4′-biphenylenedi-phosphonite.

As the phosphoric antioxidant, commercially available phosphoricantioxidants may be used, and examples include Irgafos 168 (manufacturedby Chiba Specialty Chemicals), Irgafos 12 (manufactured by ChibaSpecialty Chemicals), Irgafos 38 (manufactured by Chiba SpecialtyChemicals), ADK STAB 329K (manufactured by Asahi Denka Kogyo K.K.), ADKSTAB PEP 36 (manufactured by Asahi Denka Kogyo K.K.), ADK STAB PEP-8(manufactured by Asahi Denka Kogyo K.K.), Sandstab P-EPQ (manufacturedby Clariant), Weston 618 (manufactured by GE), Weston 619G (manufacturedby GE), Ultranox 626 (manufactured by GE), and Sumilizer GP(manufactured by Sumitomo Chemical Co., Ltd.).

As the phosphoric antioxidant, two or more kinds of phosphoricantioxidants may be used.

Among phosphoric antioxidants, tris(2,4-di-t-butylphenyl) phosphite,tetrakis(2,4-di-t-butylphenyl)-4,4′-biphenylene diphosphanite,distearylpentaerythritol diphosphite,bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite,2-[{2,4,8,10-tetra-t-butyldibenz[d,f][1.3.2]-dioxa-phosphepin-6-yl)oxy]-N,N-bis[2-[{2,4,8,10-tetra-t-butyl-dibenz[d,f][1.3.2]-dioxaphosphepine-6-yl}oxylethyl]ethaneamine,and6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[d,f][1.3.2]-dioxaphosphepineare preferable.

Examples of the sulfuric antioxidant include dialkylthiodipropionate(such as dilauryl-, dimyristyl- and distearyl-thiodipropionate); andesters of polyhydric alcohols (e.g. glycerin, trimethylolethane,trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate) withalkylthiopropionic acid (such as butyl-, octyl-, rauryl-, andstearyl-thiopropionic acid)(e.g.pentaerythryltetrakis-3-laurylthiopropionate).

Further specific examples of the sulfuric antioxidant include dilaurylthiodipropionate, dimyristyl thiodipropionate, distearylthiodipropionate, laurylstearyl thiodipropionate, and distearylthiodibutyrate.

Among them, pentaerythryltetrakis-3-lauryl thiopropionate is preferable.

As the sulfuric antioxidant, commercially available sulfuricantioxidants may be used, and examples thereof include Sumilizer TPS(manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer TPL-R(manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer TPM(manufactured by Sumitomo Chemical Co., Ltd.), and Sumilizer TP-D(manufactured by Sumitomoe Chemical Co., Ltd.).

As the sulfuric antioxidant, two or more kinds of sulfuric antioxidantsmay be used.

Examples of the amine antioxidant include a polymer of2,2,4-trimethyl-1,2-dihydroquinoline,6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline,N-(1,3-dimethylbutyl)-N′-phenyl-1,4-phenylenediamine, andN-isopropyl-N′-phenyl-1,4-phenylenediamine.

The amount of component (C) to be blended in the present composition maybe from about 0.005 to about 2 parts by weight, preferably from about0.01 to about 1 part by weight, more preferably from about 0.05 to about0.5 part by weight, relative to 100 parts by weight of component (A).

The present composition contains component (A) and component (B), andexamples of a process for preparing the composition include a method ofmelting and kneading component (A) usually at a temperature of about120° C. to 200° C. with a 5 monoaxial or a biaxial screw extruder, aBanbury mixer, a roll or various kneaders, and then mixing component (B)therewith; a method of dry-blending component (A) and component (B), andthen melting and kneading the resulting blend usually at a temperatureof about 120° C. to 150° C. with a monoaxial or biaxial screw extruder,a Banbury mixer, a roll or various kneaders. Herein, when component (B)is massive, it is preferred to conduct the mixing after being convertedinto a powder with a grinder such as a feather mill, a Nara-type grinderand an air mill, so that the melting and kneading are simplified.

In addition, when the present composition containing the component (C)is prepared, it is preferred that component (C) and component (A) areboth melted and kneaded.

Further, additives such as a phenol resin, an epoxy curing agent such asan acid anhydride, a coloring agent, an inorganic filler, a processingstabilizer, a weather resistant agent, a thermal stabilizer, an opticalstabilizer, a nucleating agent, a lubricant, a releasing agent, aflame-retardant and an antistatic agent may be contained in the presentcomposition.

When the present composition is utilized in a solder resist, in order tomask a conductive circuit on a surface of a printed circuit board, a dyeand a pigment such as phthalocyanine green and carbon black are usuallyused as a coloring agent.

An adhesive film of the present invention (hereinafter, described as thepresent adhesive film) is a mode in which the present composition ismolded into a thin layer shape (film shape) Example of the productionmethod includes:

(I) a method of extrusion-molding the present composition in a filmshape with a T-die extruder and the like;

(II) a method of extrusion-molding the present composition in a filmshape on a supporting substrate with a T-die extruder and the like;

(III) a method of laminating the film obtained by the above method (I)on a supporting substrate; and the like.

Among these, the present adhesive film obtained by the above method (II)is preferred for the use of electric and electronic parts.

Herein, a process for preparing a film obtained by extrusion molding(e.g. the above methods (I) and (II)) will be further explained below. Adistance (air gap) between a T-die and a chill roll may be about 10 cmor smaller, preferably about 8 cm or smaller, more preferably about 6 cmor smaller. When the air gap is 10 cm or smaller, there is a tendencythat film breakage and variation (dispersion) of a film thicknessgenerally called “one-side thick” are suppressed, which is preferred.

In a method by extrusion molding, the present composition is melted andkneaded, and then is extruded and molded. The melting and kneadingtemperature is preferably not lower than a melting temperature of aresin to be used, and not higher than about 120° C., and is morepreferably from about 90° C. to about 110° C. When the melting andkneading temperature is 120° C. or lower, there is a tendency that “fisheye” of the resulting adhesive film is reduced, which is preferred.

The thickness of the present adhesive film obtained by extrusion moldingmay be from about 5 μm to about 2 mm, and is preferably from 8 μm to 1mm.

Examples of the support substrate include a polyolefin film such as afilm composed of a 4-methyl-1-pentene copolymer, a cellulose acetatefilm, a releasing paper in which a silicone releasing agent or afluorine releasing agent is coated on the side thereof to be contactedwith a layer composed of a thermosetting resin composition, and areleasing polyethylene terephthalate (PET) film.

In preparation of a laminate obtained by laminating the present adhesivefilm with an adherent and thermally curing the resultant, it ispreferred that the present adhesive film is irradiated with an electronbeam before the lamination of the present adhesive film and theadherent, or after the lamination and before the thermal curing, so thatsqueeze-out of the adherent due to flowing of the resin componentderived form the present adhesive film at the thermal curing can beprevented. When electron beam irradiation is performed after thelamination of the adherent with the present adhesive film and before thethermal curing, heat resistance of the present adhesive film can beimproved in addition to the aforementioned effect of preventingsqueeze-out of the resin, which is more recommendable.

An electron beam to be used is a bundle of electrons accelerated with avoltage, and can be classified into low energy-type electron beam to beaccelerated with a voltage of around 50 to 300 kV, intermediateenergy-type electron beam to be accelerated with a voltage of around 300to 5000 kV, and high energy-type electron beam to be accelerated with avoltage of around 5000 to1000 kV. When applied to the present invention,a low energy-type electron beam may be used.

Examples of an electron accelerator include a linear cathode type, amodule cathode type, a thin plate cathode type, and a low energyscanning type.

Examples of a method of irradiating an electron beam include:

a method of irradiating an electron beam on only one side not coveredwith a support substrate in a laminate of the present adhesive film(obtained by extrusion molding) with the support substrate under inertgas atmosphere such as nitrogen;

a method of irradiating an electron beam on a side covered with thesupport substrate in the laminate;

a method of peeling off the support substrate from the laminate, and theirradiating an electron beam on one side or both sides of the presentadhesive film; and

a method of peeling off the support substrate from the laminate,laminating in advance the resulting laminate with an adherent describedbelow, and the irradiating an electron beam thereto.

An electron beam of a desired dose may be irradiated once. When anelectron beam of around 80 kGy or larger is irradiated, it is preferredto irradiate an electron beam plural times, for example, about two timesin order to maintain appearance of the adhesive film obtained afterelectron beam irradiation, or in order to increase a crosslinkingdensity of the adhesive film by the electron beam irradiation.

A total irradiation dose of an electron beam may be from about 10 toabout 300 kGy, and is preferably from about 50 to about 250 kGy. Thereis a tendency that when an irradiation dose is 10 kGy or larger, effectof opacifying a surface of an adherent upon rolling of a film at thermaladhesion and thermal curing is improved, which is preferred. There is atendency that, when the dose is 300 kGy or smaller, the adhesive film isembedded in conformity with irregularities of an adherent so thatadherability is improved, which is also preferred.

The laminate of the present invention (hereinafter, referred to as apresent laminate) is a laminate such that the present adhesive film islaminated with an adherent and is thermally cured. It is preferred toirradiate in advance an electron beam on the present adhesive filmbefore the thermal curing (which may be conducted before or afterlamination on the adherent) as described above.

As the adherent, different two or more kinds of adherents may be used.

A process for preparing the present laminate will be explained below,referring to the present adhesive film on which a support substrate islaminated as an example. Examples of the process include:

a method of peeling off a support substrate from the present adhesivefilm, laminating an adherent on both sides or one side of the presentadhesive film, and then thermally curing the resultant;

a method of laminating an adherent on a side of the present adhesivefilm on which a support substrate is not laminated, peeling off thesupport substrate from the adhesive film and, if necessary, laminatinganother adherent onto a side from which a support substrate has beenpeeled off, and then thermally curing the resultant; and

a method of laminating the present adhesive film at the side on which asupport substrate is not laminated, with an adherend, thermally curingthe resultant, and then finally peeling off the support substrate fromthe adhesive film.

Examples of thermal curing conditions for preparing the present laminateinclude a condition of maintaining a temperature of from about 100° C.to about 350° C., preferably from about 120° C. to about 300° C., morepreferably from about 160° C. to about 200° C., for the period of timefrom about 10 minutes to about 3 hours. There is a tendency that, whenthe temperature is 100° C. or higher, a thermal curing time until goodsolder heat resistance is obtained is shortened, which is preferred. Onthe other hand, when the temperature is 350° C. or lower, thermaldegradation of the present adhesive film is suppressed, which is alsopreferred.

In addition, upon thermal curing, pressurization may be performed at apressure of 0 to 6 MPa using a heatable press machine.

Examples of a material for adherent which may be used in the presentlaminate include materials which can be adhered with the presentadhesive film. Specific examples of the material include inorganicmaterials such as metals (for example, gold, silver, copper, iron, tin,lead, aluminum and silicon), glasses, and ceramics; and syntheticpolymer materials such as cellulose polymer materials (for example,paper and cloth), melamine resins, acryl-urethane resins, urethaneresins, a (meth)acryl resin, styrene-acrylonitrile copolymers,polycarbonate resins, phenol resins, alkyd resins, epoxy resins, andsilicone resins.

A material for the adherent may be a mixture or a composite materialcomposed of two or more kinds of materials. When the present laminate issuch that different two adherents are adhered via the present adhesivefilm, the materials constituting the two adherents may be the same kindmaterial or different kinds of materials.

A shape of the adherent is not particularly limited, and examplesthereof include film-like, sheet-like, plate-like, and fiber-like forms.

In addition, if necessary, the adherent may be subjected to surfacetreatment such as releasing agent treatment, covering treatment such asplating, coating treatment with a paint containing a resin compositionother than the present composition, surface modifying treatment withplasma or laser, surface oxidizing treatment, and etching.

As the adherent, electric or electronic parts such as an integratedcircuit and a printed circuit board, which are a composite material of asynthetic polymer material and a metal, are preferably used.

The following Examples further illustrate the invention in detail, butthe present invention is not limited thereto.

As components (A), (B) and (D), the following components were used. AnMFR (melt flow rate) value was measured under the conditions of 2160 gload at a temperature of 190° C., in accordance with JIS-K7210.

<Component (A)>

Component A-1:

2,4-Diamino-6-(2′-undecylimidazolyl)-ethyl-s-triazine,

(“CUREZOLE C11Z-A”, manufactured by Shikoku Kasei Co., Ltd.)

Component A-2:

An adduct of 2-phenylimidazole with isocyanuric acid,

(“CUREZOLE 2PZ-OK” manufactured by Shikoku Kasei Co., Ltd.)

Component A-3:

“K-37Y”, manufactured by P.T.I. Japan Co., Ltd. (main component:12-aminododecanoic acid)

<Component (B)>

Component B-1:

Ethylene-glycidyl methacrylate copolymer (manufactured by SumitomoChemical Co., Ltd.; content of a structural unit derived from glycidylmethacrylate: 18.0% by weight; MFR=350 g/10 min)

<Component (C)>

Component C-1:

β-(3,5-Di-t-butyl-4-hydroxyphenyl)propionic acid stearyl ester (Phenolicantioxidant, Irganox 1076; manufactured by Ciba Specialty Chemicals)

Component C-2:

Tris(2,4-di-t-butylphenyl) phosphite (Phosphoric antioxidant, Irgafos168; manufactured by Ciba Specialty Chemicals)

Component C-3:

Pentaerythryltetrakis-3-lauryl tiopropionate (Sulfuric antioxidant,Sumilizer TP-D; manufactured by Sumitomo Chemical Co., Ltd.)

EXAMPLE 1

(1) <Production Example of Thermosetting Resin Composition>

Components A-1 (1 part), B-1 (100 parts), D-1 (0.1 part), D-2 (0.1 part)and D-3 (0.05 part) were blended in dry, the resulting mixture was fedto a co-rotating biaxial extruder (L/D=42) of φ 30 mm, and wasmelt-kneaded at a screw rotational frequency of 180 rpm and a feed speedof 16 Kg/hr under a temperature of 120° C. to obtain a thermosettingresin composition.

(2) <Production Example of Adhesive Film>

Using an extruder with T-die having a diameter of 20 mm (LaboplastoMill; manufactured by TOYO Seiki Co., Ltd.), the cylinder temperature ofthe extruder was set at 100° C., the temperature of T-die was set at 90°C. and an air gap-was set at 2 cm. The thermosetting resin compositionobtained above was extruded using the above-mentioned extruder toprepare an adhesive film having a thickness of about 50 μm.

(3) <Production Example of Laminate>

Onto a printed circuit board (R-1705, a both side copper-clad laminateplate manufactured by Matsushita Electric Works, Ltd.) was used as anadherent, the adhesive film having a thickness of about 50 μm obtainedin the above-mentioned item (2) was thermally clamped under theconditions of 100° C. at 3MPa for 10 minutes, and then was thermallycured under the conditions of 180° C. at 3MPa for 60 minutes to obtain alaminate. The laminate was subjected to a solder heat resistance testand a peeling strength test below.

(4) <Solder Heat Resistance Test>

The resulting laminate was immersed in a solder bath at 260° C. for 10seconds using SOLDERABILITY TESTER EST-11 manufactured by Tabai EspecCorp. Letting this to be one cycle, 6 cycles were repeated, andappearance of the surface of the laminate was observed with naked eyes.The results are summarized in Table 1.

The result of solder heat resistance test was evaluated based on thefollowing criteria with marks ◯ and x.

◯: No abnormality (such as peeling and dilation) was observed inappearance of the thermally cured adhesive layer, and no solder grain isobserved.

x: Abnormality (such as peeling and dilation) is observed in appearanceof the thermally cured adhesive layer, or solder grain is observed.

(5) <Peeling Test>

An aluminum foil, a reinforcing material (polyethylene terephthalatefilm having a thickness of 50 μm), the adhesive film obtained in theabove-mentioned item (2), an adherent (a substrate with a copper foil;one side copper-clad laminate plate, R-1705 (FR4 printed circuit plate)manufactured by Matsushita Electric Works, Ltd.; at a side of anon-wiring pattern of the printed circuit board) and an aluminum foilwere laminated in this order, and one portion (a width of 25 mm) of theresultant was bonded by being maintained at a temperature of 180° C.under a pressure of 0.5 MPa for 60 minutes from an upper portion using aheat seal tester (manufactured by Tester Sangyo Co., Ltd.). The aluminumfoils of the resulting laminate were peeled off and the laminate wasallowed to stand for 1 hour under the conditions of a temperature of 23°C. and a humidity of 50%. Then, the laminate was cut into a piece of 10mm width x 100 mm length (adhesion length 25 mm) and a peeling test wasperformed at a peeling speed of 50 mm/sec and a peeling angle of 900under the conditions of a temperature of 23° C. and a humidity of 50%while holding a portion not bonded. The result is shown in Table 1.

EXAMPLE 2

A thermosetting resin composition, an adhesive film having a thicknessof about 50 μm and a laminate were obtained in the same manner as inEXAMPLE 1 except that 2 parts of Component A-2 was used as component(A). The results of the solder heat resistance test and the peeling testare shown in Table 1.

EXAMPLE 3

A thermosetting resin composition, an adhesive film having a thicknessof about 50 μm and a laminate were obtained in the same manner as inEXAMPLE 1 except that one part of Component A-3 was used as component(A). The results of the solder heat resistance test and the peeling testare shown in Table 1.

COMPARATIVE EXAMPLE 1

A thermosetting resin composition, an adhesive film having a thicknessof about 50 μm and a laminate were obtained in the same manner as inEXAMPLE 1 except that only Component B-1 was used without usingcomponent (A) and component (B). The results of the solder heatresistance test and the peeling test are shown in Table 1. TABLE 1Comparative Example Example 1 2 3 1 Mixing A-1 (Parts) 1 — — — ratio A-2(Parts) — 2 — A-3 (Parts) 1 B-1 (Parts) 100 100 100 100 C-1 (Parts) 0.10.1 0.1 — C-2 (Parts) 0.1 0.1 0.1 — C-3 (Parts) 0.05 0.05 0.05 — PeelingResin-clad 16.8 8.9 19.9 11.1 test copper foil (N/10 mm) FR4 substrate19.3 16.2 22.6 5.8 (N/10 mm) Solder heat resistance ◯ ◯ ◯ X test

EXAMPLE 4

(1) <Production Example of Adhesive Film Containing Support Substrate>

A cylinder temperature of an extruder equipped with φ 40 mm T-die andhaving an air gap of 4 cm was set at 100° C., and a T-die temperature ofthe extruder was set at 90° C. Subsequently, Components A-1 (1 part),B-1 (100 parts), C-1 (0.1 part), C-2 (0.1 part) and C-3 (0.05 part) weredry-blended, were fed to a co-rotating biaxial extruder (L/D=42) of d 30mm, and were melt-kneaded under a temperature of 120° C. at a screwrotation frequency of 180 rpm and a supply speed of 16 Kg/hour to obtaina thermosetting resin composition. The composition was againmelt-kneaded with the extruder, and then the thermosetting resincomposition was extrusion-molded on a side of a polyethyleneterephthalate film (X-31, manufactured by Teijin Dupont Film Co., Ltd.)on which a silicon releasing agent had been coated, to obtain abi-layered adhesive film composed of a layer having a thickness of about15 μm which dad been obtained from the thermosetting resin compositionand the polyethylene terephthalate film layer (support substrate layer).

(2) <Production Example of Laminate>

A printed circuit board (both sides copper-clad laminate plate; R-1705,manufactured by Matsushita Electric Works, Ltd.) as an adherend waslaminated on the layer obtained from the thermosetting resincomposition, of the bi-layered adhesive film obtained in the above item(1). The resulting board was thermally pressed under the conditions of100° C., 3 MPa for 10 minutes from an upper side of the supportsubstrate, and was thermally cured under the conditions for 180° C., 3MPa for 60 minutes to obtain a laminate. Subsequently, the resultinglaminate was allowed to stand for 1 hour at a temperature of 23° C. anda humidity of 50%. Thereafter, the laminate was cut into a piece of 10mm width×100 mm length, and a peeling test was performed at a peelingrate of 100 mm/sec and a peeling angle of 1800 while holding the supportsubstrate at a temperature of 23° C. and a humidity of 50%. Thepolyethylene terephthalate film layer (as a support substrate) waspeeled off at a peeling strength of 0.01 N/cm or less but the layerobtained from the adhesive film was not peeled.

As mentioned above, the thermosetting resin composition of the presentinvention can directly provide an adhesive film from the thermosettingresin composition by extrusion molding without steps of dissolution inan organic solvent, coating and drying. The laminate which is obtainedby bonding the adhesive film on an adherent is excellent in solder heatresistance and adhesive property.

By utilizing such excellent properties, the laminate of the presentinvention can be used as, for example, semiconductor encapsulatingmaterials, electronic part encapsulating materials such as solar cellsand EL (electroluminescence) lamps, die bonding sheets betweenintegrated circuit and substrate, and interlayer insulating layersbetween substrates. Further, the adhesive film can be provided for asolder resist which protects a substrate from a solder, and a protectivesheet at a production step of electronic parts.

1. A thermosetting resin composition comprising component (A) andcomponent (B) below, wherein the sum of the content of the component (A)and component (B) is 90% by weight or more based on the composition;component (A): at least one selected from amino acids and imidazoles,and component (B): an epoxy group-containing ethylene copolymer obtainedby polymerizing monomer (b₁) and monomer (b₂) below: monomer (b₁): atleast one selected from ethylene and propylene, and monomer (b₂): amonomer represented by formula (1) below:

(wherein R represents a hydrocarbon group of a carbon number of from 2to 18 having a double bond, at least one of hydrogen atoms of thehydrocarbon group may be substituted with a halogen atom, a hydroxylgroup or a carboxyl group, and X represents a single bond or a carbonylgroup.)
 2. The thermosetting resin composition according to claim 1,wherein the content of a structural unit derived from monomer (b₂) is 1to 30 parts by weight relative to 100 parts by weight of component (B).3. The thermosetting resin composition according to claim 1, wherein thecontent of a structural unit derived from monomer (b₁) is 30 to 75 partsby weight relative to 100 parts by weight of component (B).
 4. Thethermosetting resin composition according to claim 1, wherein component(B) is a copolymer obtained by polymerizing monomer (b₁), monomer (b₂)and monomer (b₃) below: monomer (b₃): a monomer which has a functionalgroup copolymerizable with ethylene, does not have a functional groupreactive with an epoxy group, and is different from either of monomer(b₁) and monomer (b₂)
 5. The thermosetting resin composition accordingto claim 1, wherein the ratio by weight of component (A) and component(B) ((A)/(B)) is from 0.1/99.9 to 10/90.
 6. The thermosetting resincomposition according to claim 1, which further contains component (C)below: component (C): an antioxidant.
 7. The thermosetting resincomposition according to claim 6, wherein component (C) is at least oneselected from the group consisting of a phenolic antioxidant, aphosphoric antioxidant and a sulfuric antioxidant.
 8. The thermosettingresin composition according to claim 1, wherein component (A) is anamino acid, and the amino acid is at least one selected from aminoaceticacid, β-alanine, 4-aminobutyric acid, aminovalerianic acid,6-aminohexanoic acid, 11-aminoundecanoic acid and 12-aminododecanoicacid.
 9. The thermosetting resin composition according to claim 1,wherein component (A) is an imidazole, and the imidazole is at least oneselected from 1-cyanoethyl-2-ethyl-4-methylimidazolium trimellitate,1-cyanoethyl-2-undecylimidazolium trimellitate,1-cyanoethyl-2-phenylimidazolium trimellitate,2,4-diamino-6-[2′-methylimidazolyl-(1′)]-ethyl-s-triazine,2,4-diamino-6-(2′-undecylimidazolyl)-ethyl-s-triazine,2,4-diamino-6-[2′-ethyl-4-methylimidazolyl-(1′)]-ethyl-s-triazine, anadduct of 2,4-diamino-6-[2′-methylimidazolyl-(1′)]-ethyl-s-triazine withisocyanuric acid, an adduct of 2-phenylimidazole with isocyanuric acid,and an adduct of 2-methylimidazole with isocyanuric acid.
 10. Anadhesive film comprising the thermosetting resin composition accordingto claim
 1. 11. The adhesive film according to claim 10, which isobtained by extrusion-molding the thermosetting resin compositionaccording to claim
 1. 12. An adhesive film, which is obtainable byfurther irradiating an electron beam on the adhesive film according toclaim
 10. 13. The adhesive film according to claim 12, which isobtainable by performing the electron beam irradiation plural times. 14.A laminate, which is obtainable by laminating the adhesive filmaccording to claim 10 or 12 with an adherent, and thermally curing theresultant.